61 アフィディコラン型およびステモダン型ジテルペンの合成研究(ポスター発表の部)
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概要
- 論文の詳細を見る
The tetracyclic enones (46 and 50), the basic skeletons of aphidicolane and stemodane diterpenes (I and II), were synthesized through an unprecedented ring construction sequence, B/C or B/D→B/C/D→A/B/C/D, and a formal total synthesis of (±)-aphidicolin (I) was accomplished. At first, the B/C/D-ring systems (18 and 22) were synthesized stereoselectively by the spiroannelation of the phenolic diazoketone (12) giving the dienone (13) followed by the regioselective reduction of the double bond by use of the neighboring hydroxyl group participation of the hydroxy-dienone (14). Next, the construction of the quarternary carbons at the C-2 position of the tricyclic compounds (18 and 22) were tried. Although the Claisen rearrangement of the II-type allyl vinyl ether (31) progressed satisfactorily to afford the rearranged product (32), the I-type product (36) could not be obtained. The construction of the I-type quarternary carbon was accomplished by the conjugate addition of Me_2CuLi to the enone (38) prepared from the tricyclic ketone (28), which was obtained through the hydrogenation of the indane ester (24). Compound 39 was transformed to the tetracyclic enone (46) via the 1,4-carbonyl transposition of 42, and compound 32 was converted to 50 via the lactone (48). Finaly, a formal total synthesis of (±)-aphidicolin (I) was accomplished by the conversion of 46 to the keto-acetonide (54), which had already been transformed to 1 in high yield by Smith et al.
- 天然有機化合物討論会の論文
- 1990-09-25
著者
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山下 博
阪大院薬
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今西 武
Faculty Of Pharmaceutical Sciences Osaka University
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井上 哲也
Faculty Of Pharmaceutical Sciences Osaka University
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亀位 勝秀
Faculty of Pharmaceutical Sciences, Osaka University
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岩田 宙造
阪大・薬
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森江 俊哉
阪大・薬
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前崎 直容
阪大・薬
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山下 博司
阪大・薬
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黒田 武志
阪大・薬
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井上 哲也
阪大・薬
-
亀位 勝秀
阪大・薬
-
今西 武
阪大・薬
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田中 徹明
阪大・薬
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金 相元
城西大・薬
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村上 和夫
城西大・薬
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村上 和夫
阪大院薬
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金 相元
Faculty Of Pharmaceutical Sciences Josai University
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森江 俊哉
Faculty Of Pharmaceutical Sciences Osaka University
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今西 武
大阪大学大学院薬学研究科
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岩田 宙造
阪大院薬
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前崎 直容
阪大院薬
-
田中 徹明
阪大院薬
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Tanaka T
Kvushu Univ. Fukuoka Jpn
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Tanaka T
Osaka Univ. Osaka Jpn
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Kim S‐w
Faculty Of Pharmaceutical Sciences Josai University
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Inoue T
Ohmiya Research Laboratory Fuji Yakuhin Co. Ltd
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Kuroda T
Faculty Of Pharmaceutical Sciences Osaka University
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Kuroda Takeshi
Faculty Of Pharmaceutical Sciences Fukuoka University
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Imanishi Takeshi
Graduate Shool Of Pharmaceutical Sciences Osaka University
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Inoue T
Osaka University Of Pharmaceutical Sciences
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Kuroda T
Faculty Of Pharmaceutical Sciences Fukuoka University
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井上 輝比古
Pharmaceutical Research Department Ube Laboratory Corporate Research & Development Ube Industrie
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Imamura T
Faculty Of Pharmaceutical Sciences Osaka University
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Murakami K
Osaka Univ. Osaka Jpn
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亀位 勝秀
Faculty Of Pharmaceutical Sciences Osaka University
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Murakami K
阪大院薬
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Inoue Takao
Faculty Of Pharmaceutical Sciences Hoshi University
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